Patent GB-698049-A (GB)
Title: New intermediate products for the production of phthalocyanines
IPC: C07D209/44
Filed: 1949-08-25
Abstract: The invention comprises compounds of the formul  <FORM:0698049/IV (b)/1> and <FORM:0698049/IV (b)/2> where R1-R3 are hydrogen or unsubstituted or substituted alkyl, aryl, aralkyl, cycloalkyl or acyl radicals, or R2 and R3 together form an alkylene or alkylidene radical; A is an unsubstituted or substituted o-arylene radical which may contain nuclear hetero atoms, or a partially hydrogenated o-phenylene radical or an o-cycloalkylene radical; B is similarly a cyclic radical in which two pairs of adjacent carbon atoms are members of the heterocyclic rings shown.  The compounds of the first formula are made by (1) reacting a dicarboxylic acid A (COOH)2 or derivative thereof still containing carboxylic groups with a substance giving off ammonia (e.g. urea, guanylurea or biuret) and a catalyst used in the phthalocyanine synthesis (e.g. a molybdate) at about 200 DEG  C. in the presence of an anion stable under the reaction conditions (e.g. nitrate, phosphate, sulphate, chloride or organic sulphonate); an inert solvent may also be present; (2) treating a dinitrile A(CN)2 or other acid derivative not containing carboxylic groups (e.g. anhydride, imide, iminoimide, amide, ureide) with ammonia or a primary or secondary amine at an elevated temperature and/or pressure, if desired in the presence of an inert solvent and an anion as above; there may also be added heavy metal salts, activated metals or metal alcoholates or amides (or materials generating these) as catalysts; such catalyst is necessary when using hydrogenated arylene dinitriles; (3) treating the alkoxy-imino-isoindolenines of Specification 698,070 with ammonia or amines, preferably below 100 DEG  C.; the reaction products of o-dinitriles with alcohols and hydrogen chloride may similarly be used and the ammonia or amine may be added to the mixture containing the dinitrile before the production of the intermediate; (4) as in (3) using the polymeric forms of the alkoxy - imino - isoindolenines; the polymeric amino-imino-isoindolenine is converted into the monomer by further treatment with ammonia or amine; (5) as in (3) using the thio analogues, such as are obtained from o-dinitriles and inorganic sulphides; (6) performing reaction (1) in the presence of a copper salt, whereby a product is obtained containing monovalent copper, and then removing the copper, e.g. by mineral acid or cyanides. When ammonia is used in the above reactions the product has hydrogen atoms in positions R1-R3; these may be exchanged for organic radicals by reaction with primary or secondary amines.  The compounds of the second formula above are obtained similarly from tetracarboxylic acids B(COOH)4 or their derivatives.  The amino-imino-isoindolenines form salts with acids and alkalis.  They combine with water and alcohols to give addition products and are slowly hydrolysed to mono-imino-imides. On prolonged heating they condense to triazine compounds, e.g. tricyano-triphenylmelamine.  Those containing free amino groups give diazoamino compounds with diazonium salts and Schiff's bases with aldehydes.  They also react with further mols. of o-dinitriles to give condensed products containing 2 or more isoindolenine nuclei.  Both the monomeric and condensed compounds form complex metal derivatives.  They are converted by reducing agents into phthalocyanines (see Specification 698,039).  In the examples, amino-imino-isoindolenine itself is made from (1) phthalic anhydride, phthalimide, imino-phthalimide or phthalamide with urea, ammonium nitrate and ammonium molybdate; (2) phthalimide with urea, ammonium molybdate and toluene-p-sulphonic acid or naphthalene-1-sulphonic acid; (3) phthalic anhydride with urea, ammonium molybdate and ammonium chloride or methanesulphonate; (4) phthalonitrile, urea and ammonium nitrate or phosphate or urea nitrate; (5) phthalic anhydride, urea, ammonium nitrate and ammonium phosphate; (6) phthalonitrile and ammonia in an autoclave with or without ammonium nitrate; (7) phthalonitrile, ammonia and sodium methoxide, with or without formic acid; (8) phthalonitrile, formamide and sodium amide; (9) phthalonitrile, formamide, ammonium nitrate and calcium methoxide or lithium ethoxide; (10) phthalonitrile, acetamide, ammonium nitrate and methanolic potash; (11) phthalonitrile, ammonia and glycol (obtained as glycol addition product); (12) phthalonitrile and alcoholic hydrogen chloride, the resulting iminoether being treated with ammonia; (13) phthalonitrile, ammonia and sodium ethoxide, the ethoxy-imino-isoindolenine (as ethanol addition product) being heated with ammonia; (14) phthalonitrile and sodium sulphide to give mercapto-imino-isoindolenine (sodium and pyridine salts described), the latter being heated with pyridine and ammonium nitrate.  In further examples the complex copper derivatives of amino-imino-isoindolenine are obtained from phthalonitrile, phthalimide and phthalic anhydride by treatment with cupric sulphate, cupric chloride, cuprous chloride, cupric nitrate, cupric acetate, copper-glycine and copper-acetylacetone; nitrogen is introduced by means of ammonia, urea or formamide; the products may contain an inorganic anion and/or a molecule of alcohol from the solvent; metal-free amino-imino-isoindolenine is obtained by treating the products with nitric acid, sulphuric acid (with or without hydrogen peroxide) or potassium cyanide.  The production of nuclear-substituted amino-imino-isoindolenines is exemplified using the following as starting materials:-4-phenoxyphthalic acid, 4 : 5-diphenylphthalic anhydride, 3 - chlorophthalic anhydride, 4 - phenylphthalimide, 3 : 4 - dicyanodiphenyl, 4 : 5 - dichlorophthalonitrile, 3 : 4 - di - cyanodiphenyl - sulphone, 2 - (31 : 41 - di-cyanophenyl) - 6 - methylbenzthiazole, 4 - methoxyphthalonitrile and 4 - methylphthalonitrile.  Similarly analogues are obtained from quinolinic acid, 4 - methyl - D 4 : 5 - tetrahydrophthalonitrile, 1 : 2 : 4 : 5 - tetracyanobenzene (prepared from pyromellitic tetraamide by conventional methods), 3 : 31 : 4 : 41-tetracyanodiphenyl and 1 : 2 - dicyanonaphthalene.  Compounds substituted on the nitrogen atom(s) are obtained as follows:-(1)1 carbaminylamino - carbaminylimino - iso - indolenine from phthalic anhydride and urea; (2) p - toluenesulphonamido - imino - iso - indolenine from phthalonitrile and p-toluenesulphonamide; (3) 1 - oxyethylamino - 3 - oxy - ethylimino-isoindolenine from phthalonitrile and ethanolamine; (4) 1-piperidino-3-imino-isoindolenine from phthalonitrile and piperidine; (5) the phenyl derivative of (4) from 3 : 4-dicyanodiphenyl and piperidine; (6) butylamino - imino - isoindolenine from phthalonitrile and n-butylamine; (7) 1-(p-sulphonamidophenylamino) - 3 - imino - isoindolenine from phthalonitrile and sulphanilamide; (8) 1-(m - or p - chlorophenylamino) - 3 - imino - isoindolenine from phthalonitrile and m- or p-chloroaniline; and (9) 1-(p-methoxyphenyl-amino) - 3 - imino - isoindolenine from phthalonitrile and p-anisidine.  In further examples, amino - imino - isoindolenine is reacted with (1) aniline to give 1-anilino-3-imino-isoindolenine or 1 - anilino - 3 - phenylimino - isoindolenine or an addition product of the latter containing a further mol. of aniline; (2) o-anisidine to give 1 - o - anisidino - 3 - imino - isoindolenine; (3) m - anisidine to give 1 - m - anisidino - 3 - (m - methoxyphenylimino) - isoindolenine; (4) cyclohexoxypropylamine to give cyclohexoxypropylamino - cyclohexoxypropylimino - isoindolenine; (5) ethanolamine to form oxyethylamino - oxyethylimino - isoindolenine; (6) p - nitraniline to yield 1 -(p - nitranilino) - 3 - (p - nitrophenylimino) - isoindolenine; (7) ethyl p - aminobenzoate to give 1 -(p - carbethoxyphenylamino) - 3 - imino - iso - indolenine; (8) acetaldehyde and benzaldehyde to give Schiff's bases; and (9) formaldehyde to give an unstated product.  In additional examples, (1) 1-anilino-3-imino-isoindolenine is obtained by heating aniline with diethoxyimino - dihydroisoindolenine (from phthalo - nitrile and ammoniacal sodium ethoxide); other amines may be used in place of aniline; the product gives self-condensation products on heating; (2) 1 - oxyethylamino - 3 - oxy - ethylimino - isoindolenine is converted into its diester with acetic anhydride; (3) 1-(m-chlorophenylamino) - 3 - imino - isoindolenine is heated with m-chloroaniline to give the 3-(m - chlorophenylimino) compound; similarly there are obtained 1-(p-chlorophenylamino)-3-(p - chlorophenylimino) - isoindolenine and 1 - (p - methoxyphenylamino) - 3 - (p - methoxy - phenylimino) - isoindolenine.  The isoindolenines are isolated as free bases or as salts, particularly nitrates.  Besides the copper derivatives there may be prepared complex nickel, cobalt and cadmium compounds.  In general, the nuclei A and B may be benzene, naphthalene, diphenyl, anthracene, pyridine or quinoline and may contain one or more substituents, e.g. chlorine, bromine, methyl, ethyl, propyl, butyl, phenyl, naphthyl, cyclohexyl, pyridyl, methoxy, ethoxy, phenoxy, methylthio, ethylthio, phenylthio, arylsulphonyl, carboxylic or sulphonic or substitution derivatives of these.  The groups R1-R3 may be methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, phenyl, naphthyl, anthraquinonyl, formyl, acetyl or their substituted derivatives.  When one of these positions is occupied by hydrogen the products may exist in tautomeric forms.  The isoindolenines may be used for preparing phthalocyanines on the fibre (see Specification 698,039).  Specification 520,415 also is referred to.  The Provisional Specification contains the subject matter of Specifications 698,039 and 698,070 and includes some further examples illustrating the following processes:-(1) preparation of monomeric and polymeric alkoxy-imino - isoindolenines from phthalonitrile and 3 : 4-dicyanodiphenyl; the alkoxy group is methoxy, ethoxy, propoxy, butoxy or amyloxy; (2) preparation f